Ethers of 9,10-dihydroxyoctadecanol



named Dec.20, 1949 2 491 533 UNITED STATES i ATENT OFFICE 2,491,533 ETHERS F 9,10-DEHYDROXYOCTADECANOL Daniel Swern, Philadelphia, Pa, assignor to the United States of America as represented by the Secretary of Agriculture No Drawing. Application January 16, 1948,

. Serial No. 2,795

13 Claims. (01. 260-615) (Granted under the act of March 3, 1883, as

amended April 30, 1928; 3'70 0. G. 757) 2 This application is made under the act of inatic hydroxy compounds, for example, phenol, March 3, 1883, as amended by the act of April cresols and the like. 30, 1928, and the invention herein described, if The octadecanol ethers of my invention are patented in any country, may be manufactured relatively stable, high boiling, waterinsoluble and used by or for the Government of the United 5 compounds which are useful as lubricants for States of America for governmental purposes delicate mechanisms, as pour-point depressants throughout the world without the payment to me and viscosity index improvers for lubricant comof any royalty thereon. positions, as plasticizers and modifiers for plastic This invention relates to ethers of long-chain compositions, as components of synthetic plastic polyhydroxy alcohols, more particularly to ethers materials and as chemical intermediates.

of 9,10-dihydroxyoctadecanol, and hasamong its The following examples are illustrative of the objects the provision of new compositions of matinvention:

ter and processes for their preparation. Other Example I objects will be apparent from the description of 28.5 g. of 9,1il-epoxyoctadecanol were dissolved the mventlon' in 114 ml. of methanol with gentle heating. The

I have found that t Of gllo'dihydmxy' solution was cooled below c. and 0.3 g. of 95% Octadecanol correspondmg to the general formula sulfuric acid added with agitation. The mixture was heated on a steam bath for two hours and a L W Q quantity of sodium bicarbonate equivalent to the 0 sulfuric acid was then added. The reaction mix- Where R is an y y haloalkenyl ture was fractionally distilled, first at atmospheric a y al, are formed on reacting 9,1 D pressure to recover unreacted methanol, and octadecanol with an orga hydroxy compound, under vacuum to isolate the ether. The latter as ow y the following equation: was dissolved in acetone, using 2-3 ml. of solvent )cngcrn)1cH-cH- cH2)10m0H 0H3:H2)1cg cH o1=n)7cH,oH ROH\ n R 0 CH (CHz)7-(]3HCH-(OH2)7CHQOH on H whereRhas the same significance as above. per gram of solute, and the solution cooled to According to the invention, 9,10-epoxyoctaabout -20 C. to precipitate the small amount d no is c d With'the y y ompound of by-product of the reaction. The precipitate by e n a mi tur of t reactants. p e a y was removed by filtration and discarded, and the in the presence o a Catalyst- UPOII Completiml solvent was evaporated from the filtrate. The of the reaction, the resulting ethers of 9,10-diresidual Oil, 9,10(l0,9) -methoxy-hydroXyoctadec-- hydroxyoctadecanol, which contains the ether anol, on redistillation, had the following characgroup linked to the ninth or tenth carbon atom, teristics:

are recovered from the reaction mixture by any 40 suitable means, as for example, by distillation and/tor solvent extraction. d430, 0 9151 Al hough the process is operative in the absence of any catalytic agent, the rate of reaction Moleculm refractlon' is greatly accelerated by the use of a catalyst. Example II Suitable catalysts include, for example, sulfuric acid, benzenesulfonic acid, toluenesulfonic acids, naphthalene sulfonic acids and similar acidic catalysts. Alkaline catalysts may also be employed but they are less effective. 0

Hydroxy compounds, suitable for use in the production of the octadecanol ethers of the in- Boiiing range: 158-161 C./0.00'7-0.008 mm. 12 1.4584

14.2 g. of 9,10-epoxyoctadecanol were dissolved in 142 g. of n-octadecanol at C. and 04.14 g. of sulfuric acid were added dropwise. The reaction mixture was heated on the steam bath for two hours and after cooling to room temperature was dissolved in ether. The ether solution was washed with water until free of sulfuric acid and ventlon include saturated aliphatic alcohols, like evaporated t dryness The residue was dissolved m hyl, e hyl, p pyl, yl. XyL yl. l y in acetone (10 ml. per gram) and the solution and octadecyl alcohols, the alkyl radical of which cooled to about -20 C. to precipitate unreacted may conta either a nflrmal a branched octadecanol, which was separated by filtration. bon atom Chain; olefinic monounsaturated alco- On evaporation of the acetone from the filtrate hols, such as allyl a coh 51 alcohols, 18 g. of a residue consisting essentially of butenyl alcohols like methallyl alcohols, and 9,10(10,9)-n-octadecoxyhydroxyoctadecanol were other alkyl-substituted allyl alcohols; and aroobtained.

Example III 49.6 gnof phenol were reacted wlth 15 g. of

9,10-epoxyoctadecanol in the presence of 0.15 g.

of 95% sulfuric acid, following the procedure described in the foregoing example, ,except--thatdistillation residue was dissolved in 95%-ethanol;

(5 ml. per gram) and after decolorization with active carbon, the solution was cooled to about rangepf temperatures withontaffecting the results. Below 60 C., however, thereaction proceeds relatively slowly, and above about 150 C.

in the presence of the acidic catalysts side re- H actions cause a reduction in yield of desired product. The preferred operating range is 60 to 100C. since. the reaction proceeds rapidly, side reactions are :ataxminimum and good yields of ethers are obtained Having thus described my invention, I claim:

1.; .An ether of dihydroxyoctadecanol corresponding to the formula:

20 C. to precipitate a small amount f by P 1 products which were removed by filtration. On CHFHJHMTH QRT evaporation of the solvent from the filtrate 13.4 wherein R15 member of th roup consisting of g Of a res1due of crude 9,10(10,9.)-phen0Xyalkyl; alkenyllhaloalkenyland aryrradi'calsv hydroxyoctadecanol were obtamed' 2. The compound of claim 1. wherein R-.;isw

alkyl. Emample'lv 3.= Thexcompound of claim-1 wherein RL-isy 9,10 (10,9) -Beta-chloroalloxyhydroxyoctadecae alkenyl; nol was prepared by reacting 9,10-ep0xy0cta- 4. The compound of claim; 1 wherein RziS decanol with beta-chloroallyl alcohol by the proaryl. cedure described in Example I. After neutraliza 5. 9,10(10,9) -Octadecoxyhydroxyoctadecanol.- tion of the catalyst with sodium bicarbonate, the 6.: 9,10(10,9) -Alloxyhydroxyoctadecanol., unreacted beta-chloroallyl alcohol was distilled '7. 9,10.(1-0,'9.)-Phenoxyhydroxyoctadecanol. off under reduced pressure and the residue was 8. .A. process of producing ethers of 9,10-didissolved in acetone (3 ml. per gram) and treated hydroxyoctadecanol comprising. reactingv 9,10- with activated carbon for one hour. The solution epoxyoctadecanol with. a hydroxy compound of was filtered, cooled to about -20 C. and the the formula R-OI-I, wherein .Rais a;,.member,.of small amount of precipitate which formed was.. the group consisting of alkyl, alkenyl,;haloalk.enyl filtered off and. discarded. The acetone was dis-. and :aryl radicals. tilled from the filtrate yielding crude 9,10(10,9)- 9; The process of'claim 8wherein-R is .octadecyl. beta-chloroalloxyhydroxyoctadecanol. 10. The process of claim 8 wherein R is allyl.

Examplav 11. The process of claim 8 wherein R, is phenyl.

12. A process of producing ethers of 9,10-di- A number of ethers. of 9,'1 -d1hydr0 y0cta-. hydroxyoctadecanol. comprising reacting. 9,10. decanol formed by interaction of the corre--. epoxyoctadecanolwith.a hydroxy..compound of sp n alcohol w ,1 p y d ano1. the formula a-on, wherein'R is a member 10f; Were p epared by e p oc d sc b H1140 the group consisting of alkylgalk'enyl haloalkenyl. Example I. The characteristics of some of these and aryl radicals, in the presence of a reaction compounds are listed in the following tablez catalyst.

Boiling Range no" (1 gggggg gfi 9,10(10,9)-ethoxyhydroxyoctadecauol... 179-185 O1./O.005-O.01 mm 1. 4565' 99.7 9,10(10,9)-n-propoxyhydroxyocatdecanol.- 156168 O./0.0050.0l mm 103.0 9,10(10,9)-n-butoxyhydroxy0ctadecanol l70175 C./0.007. mm. 108.3 9,10(10,9)-iso-butoxyhydroxyoctadecauol 163-l70 C./0.0070.02 mm 108.3 9,10(10,9)-alloxyhydroxyoctadecanol l7l.l8'8 C./0.02-0.03 mm 1029 Similar results were .obtained using other cat-1 13..The process of claim l2wherein the reaction. alysts, such as benzenesulfonic acid, toluenesulcatalyst is sulfuric acid... fonic acid, naphthalene-Z-sulfonic acid and hy- DANIEL SWERN.

drogen chloride in place of sulfuric. acid and heating the mixture at reaction temperature for;- a length of time sulficient to bring the reaction cresols and the like.

The reaction may be conducted over, a wide such as butenyl' alooholsg, hexyl, heptyl, octyl, lauryl alcohol, oleylialcoholi REFERENCES "CITED The following; references are of record in :the

file .of this-patent: 0.0

UNITED STATES PATENTS 

